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At least 127 records · Page 7

The design, construction and testing of the optics for a 147-cm-aperture telescope

Geodetic optics research for the Air Force Cambridge Research Laboratories (AFCRL) is described. The work consisted mainly of the fabrication of the optical components for a telescope with a 152-cm-diam (60-in.) primary mirror masked down to 147-cm-diam for use by the AFCRL for a lunar ranging experiment. Among the achievements of this contract were the following: completion of the primary and secondary mirrors for a high-quality 147-cm-diam telescope system in eight months from the start of edging the primary; manufacture and testing of a unique center mount for the primary according to an AFCRL design that allowed for a thin-edged and therefore less-massive mirror; and development of a quantitative analysis of the wire test for calculating the departure of the mirror figure from the design figure quickly and accurately after each polishing step. This analysis method in conjunction with a knowledge of polishing rates for given weights and diameters of tools, mirror, and polishing materials should considerably reduce the polishing time required for future large mirrors.

Buchroeder, R. A.↗

Radiative amplification of sound waves in the winds of O and B stars

The velocity perturbation associated with an outwardly propagating sound wave in a radiation-driven stellar wind gives rise to a periodic Doppler shifting of absorption lines formed in the flow. A linearized theory applicable to optically thin waves is used to show that the resulting fluctuation in the absorption-line force can cause the wave amplitude to grow. Detailed calculations of the acceleration due to a large number of lines indicate that significant amplification can occur throughout the high-velocity portion of winds in which the dominant force-producing lines have appreciable optical depths. In the particular case of the wind of Zeta Pup (O4f), it is found that the e-folding distance for wave growth is considerably shorter than the scale lengths over which the physical properties of the flow vary. A qualitative estimate of the rate at which mechanical energy due to nonlinear waves can be dissipated suggests that this mechanism may be important in heating the supersonic portion of winds of early-type stars.

Macgregor, K. B.↗

A HTAP Multi-Model Assessment of the Influence of Regional Anthropogenic Emission Reductions on Aerosol Direct Radiative Forcing and the Role of Intercontinental Transport

In this study, we assess changes of aerosol optical depth (AOD) and direct radiative forcing (DRF) in response to the reduction of anthropogenic emissions in four major pollution regions in the northern hemisphere by using results from 10 global chemical transport models in the framework of the Hemispheric Transport of Air Pollution (HTAP). The multi-model results show that on average, a 20% reduction of anthropogenic emissions in North America, Europe, East Asia and South Asia lowers the global mean AOD and DRF by about 9%, 4%, and 10% for sulfate, organic matter, and black carbon aerosol, respectively. The impacts of the regional emission reductions on AOD and DRF extend well beyond the source regions because of intercontinental transport. On an annual basis, intercontinental transport accounts for 10-30% of the overall AOD and DRF in a receptor region, with domestic emissions accounting for the remainder, depending on regions and species. While South Asia is most influenced by import of sulfate aerosol from Europe, North America is most influenced by import of black carbon from East Asia. Results show a large spread among models, highlighting the need to improve aerosol processes in models and evaluate and constrain models with observations.

Yu, Hongbin↗

Measurement of Cohesion in Asteroid Regolith Materials

A study has been initiated to examine cohesive forces in asteroid materials to contribute to a better understanding of low density bodies such as asteroids and Phobos, and assist in exploration missions involving interaction with their surface material. The test specimen used in this study was a lightly weathered CM2 meteorite which is spectroscopically similar to Type C (carbonaceous) asteroids, and thought to have representative surface chemistry. To account for sample heterogeneity, adhesion forces were measured between the CM2 sample and its five primary mineral phase components. These adhesive forces bound the range of cohesive force that can be expected for the bulk material. All materials were characterized using a variety of optical and spectroscopic methods. Adhesive forces on the order of 50 to 400 μN were measured using a torsion balance in an ultrahigh vacuum chamber. The mineral samples exhibited clearly different adhesive strengths in the following hierarchy: Serpentine > Siderite > Bronzite > Olivine ≈ Fe-Ni.

Asteroids↗

Nano-Newton Electrostatic Force Actuators for Femto-Newton-Sensitive Measurements: System Performance Test in the LISA Pathfinder Mission

Electrostatic force actuation is a key component of the system of geodesic reference test masses (TM) for the LISA orbiting gravitational wave observatory and in particular for performance at low frequencies, below 1 mHz, where the observatory sensitivity is limited by stray force noise. The system needs to apply forces of order 10 −9 N while limiting fluctuations in the measurement band to levels approaching 10 −15 N=Hz 1/2 . We present here the LISA actuation system design, based on audio-frequency voltage carrier signals, and results of its in-flight performance test with the LISA Pathfinder test mission. In LISA, TM force actuation is used to align the otherwise free-falling TM to the spacecraft-mounted optical metrology system, without any forcing along the critical gravitational wave-sensitive interferometry axes. In LISA Pathfinder, on the other hand, the actuation was used also to stabilize the TM along the critical x axis joining the two TM, with the commanded actuation force entering directly into the mission’s main differential acceleration science observable. The mission allowed demonstration of the full compatibility of the electrostatic actuation system with the LISA observatory requirements, including dedicated measurement campaigns to amplify, isolate, and quantify the two main force noise contributions from the actuation system, from actuator gain noise and from low frequency “in band” voltage fluctuations. These campaigns have shown actuation force noise to be a relevant, but not dominant, noise source in LISA Pathfinder and have allowed performance projections for the conditions expected in the LISA mission.

M. Armanos↗

Radiative Forcing by Contrails

A parametric study of the instantaneous radiative impact of contrails is presented using three different radiative transfer models for a series of model atmospheres and cloud parameters. Contrails are treated as geometrically and optically thin plane parallel homogeneous cirrus layers in a static atmospheres The ice water content is varied as a function of ambient temperature. The model atmospheres include tropical, mid-latitude, and subarctic summer and winter atmospheres Optically thin contrails cause a positive net forcing at top of the atmosphere. At the surface the radiative forcing is negative during daytime. The forcing increases with the optical depth and the amount of contrail cover. At the top of the atmosphere a mean contrail cover of 0.1% with average optical depth of 0.2 to 0.5 causes about 0.01 to 0.03 W/m(exp 2)a daily mean instantaneous radiative forcing. Contrails cool the surface during the day and heat the surface during the night, and hence reduce the daily temperature amplitude The net effect depends strongly on the daily variation of contrail cloud cover. The indirect radiative forcing due to particle changes in natural cirrus clouds may be of the same magnitude as the direct one due to additional cover.

Meerkoetter, R.↗

Ferroelectricity in a semiconducting all-inorganic halide perovskite

Ferroelectric semiconductors are rare materials with both spontaneous polarizations and visible light absorptions that are promising for designing functional photoferroelectrics, such as optical switches and ferroelectric photovoltaics. The emerging halide perovskites with remarkable semiconducting properties also have the potential of being ferroelectric, yet the evidence of robust ferroelectricity in the typical three-dimensional hybrid halide perovskites has been elusive. Here, we report on the investigation of ferroelectricity in all-inorganic halide perovskites, CsGeX 3 , with bandgaps of 1.6 to 3.3 eV. Their ferroelectricity originates from the lone pair stereochemical activity in Ge (II) that promotes the ion displacement. This gives rise to their spontaneous polarizations of ~10 to 20 μC/cm 2 , evidenced by both ab initio calculations and key experiments including atomic-level ionic displacement vector mapping and ferroelectric hysteresis loop measurement. Furthermore, characteristic ferroelectric domain patterns on the well-defined CsGeBr 3 nanoplates are imaged with both piezo-response force microscopy and nonlinear optical microscopic method.

36 MATERIALS SCIENCE↗

Results of the Compensated Earth-Moon-Earth Retroreflector Laser Link (CEMERLL) Experiment

Adaptive optics techniques can be used to realize a robust low bit-error-rate link by mitigating the atmosphere-induced signal fades in optical communications links between ground-based transmitters and deep-space probes. Phase I of the Compensated Earth-Moon-Earth Retroreflector Laser Link (CEMERLL) experiment demonstrated the first propagation of an atmosphere-compensated laser beam to the lunar retroreflectors. A 1.06-micron Nd:YAG laser beam was propagated through the full aperture of the 1.5-m telescope at the Starfire Optical Range (SOR), Kirtland Air Force Base, New Mexico, to the Apollo 15 retroreflector array at Hadley Rille. Laser guide-star adaptive optics were used to compensate turbulence-induced aberrations across the transmitter's 1.5-m aperture. A 3.5-m telescope, also located at the SOR, was used as a receiver for detecting the return signals. JPL-supplied Chebyshev polynomials of the retroreflector locations were used to develop tracking algorithms for the telescopes. At times we observed in excess of 100 photons returned from a single pulse when the outgoing beam from the 1.5-m telescope was corrected by the adaptive optics system. No returns were detected when the outgoing beam was uncompensated. The experiment was conducted from March through September 1994, during the first or last quarter of the Moon.

Wilson, K. E.↗

Transverse strain measurements using fiber optic grating based sensors

A system and method to sense the application of transverse stress to an optical fiber which includes a light source that producing a relatively wide spectrum light beam. The light beam is reflected or transmitted off of an optical grating in the core of an optical fiber that is transversely stressed either directly or by the exposure to pressure when the fiber is bifringent so that the optical fiber responds to the pressure to transversely stress its core. When transversely stressed, the optical grating produces a reflection or transmission from the light beam that has two peaks or minimums in its frequency spectrum whose spacing and/or spread are indicative of the forces applied to the fiber. One or more detectors sense the reflection or transmissions from the optical grating to produce an output representative of the applied force. Multiple optical gratings and detectors may be employed to simultaneously measure temperature or the forces at different locations along the fiber.

Udd, Eric↗

Temperature controlled transformations of giant unilamellar vesicles of amphiphilic triblock copolymers synthesized via microfluidic mixing

We report on a simple approach for synthesis of temperature-responsive giant unilamellar vesicles (GUVs) from poly(N-vinylcaprolactam) 15 -block-poly(dimethylsiloxane) 65 -block-poly(N-vinylcaprolactam) 15 (PVCL 15 -PDMS65-PVCL 15 ) triblock copolymer and non-temperature responsive small and giant vesicles from novel poly(N-vinylpyrrolidone)-block-poly(dimethylsiloxane)-block-poly(N-vinylpyrrolidone) (PVPON 15 -PDMS 65 -PVPON 15 and PVPON 6- PDMS 30- PVPON 6 ) triblock copolymers using microfluidic mixing at 25 °C. We show that temperature-responsive PVCL 15 -PDMS 65- PVCL 15 GUVs with the average diameter of 1.4 ± 0.2 µm while being stable at room temperature for at least 14 days, transformed irreversibly into small vesicles of 168 ± 40 nm after incubation of their aqueous solution at 42 °C for 24 h. We hypothesized that this transformation is induced by local compressive stresses of the vesicle membrane due to the collapse of PVCL blocks above the copolymer lower critical solution temperature (LCST) leading to the decrease of the vesicle membrane thickness. Consequently, we found that the temperature-induced size transformation of the PVCL-based GUVs at 42°C can be suppressed by substituting PVCL with its hydrophilic homologue PVPON, or by suppressing the PVCL's LCST behavior through hydrogen-bonding with tannic acid molecules. In the former case, novel PVPON n -PDMS m -PVPON n triblock copolymers (n = 15, m = 65 and n = 6, m = 30) assemble into vesicles stable from 25 °C to 55 °C as confirmed by optical and electron microscopy, dynamic light scattering (DLS) and small-angle neutron scattering (SANS). In the latter, hydrogen bonding interactions of PVCL with the polyphenol tannic acid (TA) at room temperature resulted in stable PVCL-based GUVs at 42°C as confirmed by optical, electron, and atomic force microscopies. We also found that physical crosslinking of the PVCL corona through hydrogen bonding with TA in PVCL 15- PDMS 65- PVCL 15 GUVs will delay their low pH-induced degradation at 37°C by 48 h compared to non-modified GUVs. Our findings open opportunities for the development of temperature-regulated stable micro-vehicles that would change their structural characteristics in the physiologically relevant temperature range from 25 to 42°C and can be utilized for cell mimicking studies. The developed GUVs also have potential in theranostic drug delivery as substitutes for polymer microcapsules and lipid microbubbles as well as for stimuli-triggered sensing, protection, and rapid response in an aqueous environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Initial Laboratory Measurements Probing Hydrogen Interactions with Eagle Ford Shale and Pyrite: Potential Implications for Subsurface Hydrogen Storage

Hydrogen (H 2 ) has the potential to be a transformative technology as an enabler to a low-carbon future and promoter of renewable energy. When H 2 is injected and stored in the subsurface, it has the potential to interact with the caprock (usually shale) which overlies and seals the storage reservoir. Here, this study examines geochemical reactions or changes in surface morphology to Eagle Ford Shale, a proxy for caprock, upon exposure to H 2 at 50°C and 10.3 MPa. Reactions were also performed with N 2 to provide an experimental control. Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), Atomic Force Microscopy (AFM), and Optical Photothermal-Infrared (O-PTIR) Spectroscopy were applied to quantify changes on the microscale and nanoscale level. Fluid chemistry changes were monitored with Ion Chromatography (IC) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Exposure of Eagle Ford Shale to H 2 gas alone did not result in any alterations to the shale chemically or any changes in the surface morphology. Exposure of Eagle Ford Shale to both H 2 and water as well as N 2 and water resulted in changes to the surface morphology because of gypsum dissolution and reprecipitation, thus indicating that H 2 is not necessary to promote changes. Pure pyrite was the most reactive with H 2 possibly resulting in a reduction to pyrrhotite. These initial studies suggest that the extent of reactions activated by hydrogen with caprock are minor under the temperature and pressure conditions that would represent underground hydrogen storage.

08 HYDROGEN↗

Promotion of CaCO 3 Nucleation by Carboxyl- and Amine-Terminated Peptoid Nanotubes

The use of surfaces to promote heterogeneous nucleation of CaCO 3 has been extensively studied to better understand natural processes of biomineralization, to develop bioinspired approaches for synthesizing composite materials with diverse functionalities, and as a route toward accelerating CO 2 mineralization. Peptoids have emerged as a material of particular interest, because they offer tunable side chain chemistry while maintaining a constant long-range self-assembled architecture. Here, in this work, we investigate the ability of films of self-assembled -NH 2 and −COOH terminated peptoid nanotubes to promote the nucleation of CaCO 3 . Using a combination of atomic force, scanning electron, and optical microscopy, we find that interwoven films of nanotubes formed from peptoids with -NH 2 side chains promote the preferential formation of vaterite with the (001) plane parallel to the film and exhibit a lower interfacial energy than that reported for inorganic surfaces. In contrast, the film of −COOH-functionalized peptoid nanotubes is a much stronger promoter, giving a particle density 5 orders of magnitude larger than for the -NH 2 terminated peptoid nanotubes and enabling complete coverage of individual peptoid tubes with CaCO 3 nanoparticles that results in a composite material with a 50-fold increase in Young’s modulus. Thus, interwoven films of peptoid nanotubes provide a useful platform for investigating the impact of specific chemical groups on nucleation and offer potential application to accelerated mineralization of CO 2 for removal from the environment or modulation of mineralogy and properties of carbonate-based building materials.

carbon nanotubes↗

Domain-Dependent Surface Adhesion in Twisted Few-Layer Graphene: Platform for Moiré-Assisted Chemistry

Twisted van der Waals multilayers are widely regarded as a rich platform to access novel electronic phases thanks to the multiple degrees of freedom available for controlling their electronic and chemical properties. Here, in this work, we propose that the stacking domains that form naturally due to the relative twist between successive layers act as an additional ”knob” for controlling the behavior of these systems and report the emergence and engineering of stacking domain-dependent surface chemistry in twisted few-layer graphene. Using mid-infrared near-field optical microscopy and atomic force microscopy, we observe a selective adhesion of metallic nanoparticles and liquid water at the domains with rhombohedral stacking configurations of minimally twisted double bi- and trilayer graphene. Furthermore, we demonstrate that the manipulation of nanoparticles located at certain stacking domains can locally reconfigure the moiré superlattice in their vicinity at the micrometer scale. Our findings establish a new approach to controlling moiré-assisted chemistry and nanoengineering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling the Degradation Mechanism of High-Temperature Superconductor Bi 2 Sr 2 CaCu 2 O 8+δ in Water-Bearing Environments

We report the physical properties of copper oxide high-temperature superconductors have been studied extensively, such as its band structure, and doping effects of Bi 2 Sr 2 CaCu 2 O 8+δ (Bi-2212). However, some chemical-related properties of these superconductors are rarely reported, such as their stability in air. Here, we report experiments combined with ab initio calculations that address the effects of water in contact with Bi-2212. The evolution of Bi-2212 flake with exposure to water for different time intervals were tested and characterized by optical microscopy (OM), atomic force microscopy (AFM), Raman spectroscopy, transmission electron microscopy (TEM) and electrical measurements. The thickness of Bi-2212 flakes is gradually decreased in water, and some thin flakes can be completely etched away after a few days. The stability of Bi-2212 in other solvents is also evaluated, including alcohol, acetone, HCl and KOH. The morphology of Bi-2212 flakes is relatively stable in organic solvents. However, the flakes are etched relatively quick in HCl and KOH, especially in acidic environment. Our results imply that hydrogen ion is primarily responsible for the deterioration of their properties. Both TEM and calculation results demonstrate that the atoms in Bi-O plane is relatively stable when compared to the inner atoms in Sr-O, Ca-O and Cu-O planes. This work contributes towards understanding the chemical stability of Bi-2212 superconducting device in environmental medium, which is important for both fundamental studies and practical applications of copper oxide high-temperature superconductors.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quantifying the Influence of Defects on Selectivity of Electrodes Encapsulated by Nanoscopic Silicon Oxide Overlayers

Encapsulation of electrocatalysts and photocatalysts with semipermeable nanoscopic oxide overlayers that exhibit selective transport properties is an attractive approach to achieve high redox selectivity. However, defects within the overlayers-such as pinholes, cracks, or particle inclusions-may facilitate local high rates of parasitic reactions by creating pathways for facile transport of undesired reactants to exposed active sites. Scanning electrochemical microscopy (SECM) is an attractive method to determine the influence of defects on macroscopic performance metrics thanks to its ability to measure the relative rates of competing electrochemical reactions with high spatial resolution over the electrode. Here, we report the use of SECM to determine the influence of overlayer defects on the selectivity of silicon oxide (SiOx) encapsulated platinum thin-film electrocatalysts operated under conditions where two competing reactions-the hydrogen evolution and Fe(III) reduction reactions-can occur. After an SECM methodology is described to determine spatially resolved selectivity, representative selectivity maps are correlated with the location of defects that are characterized by optical, electron, and atomic force microscopies. This analysis reveals that certain types of defects in the oxide overlayer are responsible for ∼60-90% of the partial current density toward the undesired Fe(III) reduction reaction. By correcting for defect contributions to Fe(III) reduction rates, true Fe(III) permeability values for the SiOxoverlayers were determined to be over an order of magnitude lower than permeabilities determined from analyses that ignore the presence of defects. Lastly, different types of defects were studied revealing that defect morphology can have varying influence on both redox selectivity and calculated permeability. This work highlights the need for spatially resolved measurements to evaluate the performance of oxide-encapsulated catalysts and understand their performance limits.

25 ENERGY STORAGE↗

Microphysical properties of atmospheric soot and organic particles: measurements, modeling, and impacts

Atmospheric soot and organic particles from fossil fuel combustion and biomass burning modify Earth’s climate through their interactions with solar radiation and through modifications of cloud properties by acting as cloud condensation nuclei and ice nucleating particles. Recent advancements in understanding their individual properties and microscopic composition have led to heightened interest in their microphysical properties. This review article provides an overview of current advanced microscopic measurements and offers insights into future avenues for studying microphysical properties of these particles. To quantify soot morphology and ageing, fractal dimension ( D f ) is a commonly employed quantitative metric which allows to characterize morphologies of soot aggregates and their modifications in relation to ageing factors like internal mixing state, core-shell structures, phase, and composition heterogeneity. Models have been developed to incorporate D f and mixing diversity metrics of aged soot particles, enabling quantitative assessment of their optical absorption and radiative forcing effects. The microphysical properties of soot and organic particles are complex and they are influenced by particle sources, ageing process, and meteorological conditions. Furthermore, soluble organic particles exhibit diverse forms and can engage in liquid–liquid phase separation with sulfate and nitrate components. Primary carbonaceous particles such as tar balls and soot warrant further attention due to their strong light absorbing properties, presence of toxic organic constituents, and small size, which can impact human health. Future research needs include both atmospheric measurements and modeling approaches, focusing on changes in the mixing structures of soot and organic particle ensembles, their effects on climate dynamics and human health.

54 ENVIRONMENTAL SCIENCES↗

Classical vs. quantum plasmon-induced molecular transformations at metallic nanojunctions

Chemical transformations near plasmonic metals have attracted increasing attention in the past few years. Specifically, reactions occurring within plasmonic nanojunctions that can be detected via surface and tip-enhanced Raman (SER and TER) scattering were the focus of numerous reports. In this context, even though the transition between localized and nonlocal (quantum) plasmons at nanojunctions is documented, its implications on plasmonic chemistry remain poorly understood. We explore the latter through AFM-TER-current measurements. We use two molecules: i) 4-mercaptobenzonitrile (MBN) that reports on the (non)local fields and ii) 4-nitrothiophenol (NTP) that features defined signatures of its neutral/anionic forms and dimer product, 4,4′-dimercaptoazobenzene (DMAB). The transition from classical to quantum plasmons is established through our optical measurements: It is marked by molecular charging and optical rectification. Simultaneously recorded force and current measurements support our assignments. In the case of NTP, we observe the parent and DMAB product beneath the probe in the classical regime. Further reducing the gap leads to the collapse of DMAB to form NTP anions. The process is reversible: Anions subsequently recombine into DMAB. Our results have significant implications for AFM-based TER measurements and their analysis, beyond the scope of this work. In effect, when precise control over the junction is not possible (e.g., in SER and ambient TER), both classical and quantum plasmons need to be considered in the analysis of plasmonic reactions

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗